DE1592904A1 - Process for improving pigments - Google Patents

Description

PATINTANWXLTb DR. E. WIEGAND DIPL-ING. W. NIEAAANN 1 ζ 9? Q Π ' DR. M. KÖHLER DIPL-ING. C GERNHARDT ' ^{Ό C 3 U} ~ ^r MÖNCHEN HAMBURG TELEPHONE: 555 476 8000 MDN CHEN 1 5, 19 · AUS · 1300 TELEGRAMS: KARPATENT NUSSBAUMSTRASSE 10

V. 12 7Ob / 66 15 / We

Laporte Titanium Limited, LQWlGM (England)

Process for improving pigments

The invention relates to a method of treating pigments and, more particularly, to treatment a pigment to improve the gloss and / or deodorant properties of a paint or a coating or varnish in which the pigment is incorporated and also to improve the water-dispersibility of the pigment and / or its dispersibility in the paint or the laok medium.

BATH ORIGINAL

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_ 2 -

According to the invention, a method for treating a pigment is created in which κ is in contact with the pigment particles with a compound of the cycloalkane series containing a hydroxyl group bonded directly to a carbon atom and r: at least two Ilydroxya; .. kyl groups brings. The compound can be used in an amount of from 0.01 to 5 ¹ Å, preferably from 1 to 1.0%, based on the weight of the pigment. The substituted cycloalkane compounds used in accordance with the invention can contain further substituents, in particular IIalo, rena, ocer alkyl or amino groups ^: md the Oycloalkankern can have more than one hydroxy-substituted carbon atom, furthermore any one of the carbon atoms in the Oycloalkanring can have one or especially two Carry hydroxyalkyl groups, and the hydroxyl group or groups, the Ilydroxyalkyigruppen and other substituents can be in any positions in the Oycloalicanring, but preferably at least one hydroxyalkyl group is bonded to a ring carbon atom adjacent to a hydroxyl group-bearing carbon atom. Polyalkylolcyclohexanols and polyalkylolcyclopentanols are very particularly suitable. The alkylene radicals in the

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Alkylol group; .-inc preferably lower .ulkylenreste with ■ a salary ar. up to 3 foal fuel atoms, in particular 'rlutli /] en.-rupren, uiiG dia connections can z.l>. :-:;'egg, contain three or in particular four AlJ-tylolgruppen. the Alkyl radicals in the Allc'lol-Rrurper can be identical or different be it.

^ ei cei \ procedure genus der iJrfinuung v / ground vorzu ^ sweipe the pi _; : r.ier: tteilcher nit a verbinamv; the general j'ovuei

^ t ₀ _ _R _ (G ₁ J. ^ iiTi ^,

brought into üer'.ihx'un ^, ii: va.lci.er R a Cyclop en ty I- or Oyolo ^ e.xylrsiit d .α-represents, η 1, 1 your 3, m 2, '5 or 4 is,; 3ie ", 'drc ^ yl-rur.pe: -iui' the left ¹ : 3 side of the pcrmel is bound directly to a Rin ^ r.oLlenstüfi'aiom and in '.vuluher ΊΙ v / pus ö ü üsΐitue: jteη, ir, especially Alky 1 grupr ei: er. can hold. A] s connections ae: ¹ understanding general Forrael can especially those of the Jormulas

C.

II C

HO (CH ₉ )

2 ^J x

N ₃ ^

H OE

009887/161 1

in which P ^, R ₂ and K ^ represent hydrogen or alkyl radicals and χ is 1, 2 or 3.

Particularly advantageous compounds are 2,2,6,6-tetramethylol-cyclohexanol and 2,2,6,6-tetramethylol-4-meth, loyclohexanol. Other preferred compounds that can be used are 2,2,5,5-ietramethylolcyclopentanol, 2,2,6,6-tetramethylol-3,4-dimethyl-cyclohexanol and 2,2,6,6-tetra- (3'-hydroxypropyl) - cycloheKanol is mentioned ₀

The production of 2,2,6, o-tetramethylolcyclohexanol is described in "Organic Syntheses" Collective Volume 4, Editor-in-Chief ITorman Kabjohn, (edited by John l.iley tz öcrs Ine) on pages 907 and 90S.

Those to be treated advantageously according to the invention Pigments include 'litanciioxyd and can anatase or ii Titanium dioxide, a compound pigment with a JeI.y on titanium dioxide or a colored pigment rr.it with oeiirlt to be on 'iitanö-ioxyd. L'as anatas-ocer rutile-i: tandioxyd came: be pure, but preferably small I; enr; en on hydrating metal oxides, see B. hydrated alumina or a hydrated titanium oxide on the surface of the particles are present. Other pigments that can be treated by the method according to the invention,

009 _{887/1611 8AD} original

include silicon dioxide, barium sulfate (blanc fixe), Lithopon, barium carbonate, zirconium oxide, zinc oxide, aluminum oxide, Chrome yellow and phthalocyanine.

The pigment particles are preferably mixed with a compound in the liquid state, e.g. with a compound that is itself a liquid or with a solution aer (solid or liquid) compound in a suitable solvent such as an alcohol, acetone or water treated. In the case of treatment with a solution, the solvent is then removed from the treated particles removed.

The pigment particles can be dry before the treatment, but they are advantageously mixed with water Formation of a paste, slurry, or slurry mixed. The particles, on the other hand, can be mixed with a dispersion of a liquid compound in another liquid be treated.

The mixture should be stirred to ensure uniform distribution of the compound added. It is a thorough mixture of the pigment particles or the paste, slurry or slurry of the particles and water with the compound or with the solution of the

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Connection necessary to all particles in essence treat uniformly and such mixing depends not necessarily just dependent on the length of the mixing operation; also the type of mixing device and the extent of mixing are essential factors to be considered.

After having brought the connection with the pigment particles in r> ESS affecting, the particles are preferably at a temperature within a range of 10O ⁰ C to 180 ⁰ O, advantageously within the range of 105 0 to 150 G dried, but with the precaution that the selected temperature is not so high,

that a burning or charring occurs by what a Ver
! örrtlcolouring of the pigment causes. The drying removes any water from the particles which may be present along with the organic solvent or the compound if an organic solution was used. In addition, drying can remove some of the compound if the compound is volatile at the drying temperature. Subject to drying, the treated particles can be ground to break up any agglomerates of the particles that may have formed.

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The method of treating a pigment advantageously comprises adding the compound to a slurry of surface-coated titanium dioxide, the surface of which is e.g. is associated with aqueous oxides of aluminum and titanium, the pesticide content of the pulp being in the range of 50 to 65 Gev .'.-vo, preferably before about 60 G-ew.-yj. Itfenn is the Peststoffgehalt at the lower limit of this Lereiches, it is necessary to stir aer drying while, un far ^ eherde changes in the distribution d it: "Ui" eg flat V he υ incur, - ¹ to the dried solid. Avoid mixing the added cycloalkai derivative uno. 'Iit: -nciiox ^ dbreies can expediently be carried out in a paste mixer, if a number of solids are used v; ji'G, im Ilir.blick aui 'üi e high viscosity of oyatein.].) TiS J3e``H; iulungs; .iit'.ül i ^ uir e ": tveder :: u the" rei before the icing: .un.;: or zv. "ccKn;'iiiiger can be added directly into the mixing device," - the Hischseit should last, for example, 5 to 60 minutes, although the preferred speed of the performance or HischeinriciituiiK; auirlngt. It was found that an I-II time of 30 hours is generally suitable.

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The connection is expediently in the course a "known way of working for Über2ugsbilaung a surface after the titanium dioxide, whose surface hydrate with aluminum or titanium oxides and -e.g. Silicone bonded, washed essentially free of soluble salts and partially dried to a filter cake of about 60 wt .- ^ solids content result.

The titanium dioxide particles used in the methods of the refining must of course be treated in accordance with the invention after any operation has been carried out, such as e.g. ÜKlcinierung would destroy the ^r jL'eilchen of, when executed after the treatment, the effect of the compound on the particles. The Titancioxydteilchen are preferably of a classification ~ c ycle _c ~: sbeharidlun _t ": subjected to particles tiit GröiJen:; ut -. - parlous to receive within a certain range, the Tit be ^ naioxydteilchen eggs advantageously after classifi ^ ierungsbehanulung and, On the other hand, the particles can be treated during a wet milling process and then dried.

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The invention also provides a pigment which Pigment particles with a compound of the cycioalkane series retained thereon with a directly attached to a king carbon atom bonded hydroxyl group in the α at least 2 hydroxyalkyl groups, in particular a compound of general l'ormel

in which E represents a cyclopentyl or cyclohexyl radical, η 1,2 ο which is 3, m 2,3 or 4 and the hydroxyl group on the left-hand side of the formula is bonded directly to a ring carbon atom and in which R further ubstituer.ten, in particular May contain alkyl groups. The invention also provides a pigment whose particles have been brought into contact with a compound as defined above. The invention further provides a paint or varnish with a casing -> .n a pigment, according to the invention, and the pigment advantageously comprises sitanic oxide.

1 / The following examples serve to explain the Invention.

In the examples is 2,2,6,6-tetramethylolcyclohexanol short as "Ϊ.Μ.Ο." and 2,2,6, b-tetramethylol-4-

BATH ORIGINAL

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- ίο -

methylcyclohexanol as "i'.K.R.C." ceseichnet. Of the "fo-gloss" value and opacity were as in the US application k-4 143/64 described, determines "

example 1

Sin Hutil titanium oxide pigment is provided with a surface coating in a known manner, so that hydrated silicon dioxide and hydrated aluminum oxide with the surface of this pigment in a 0.5 ^c / o SiOp and 1.0 ) j AL-O- ^, drawn to the weight of the pigment, equivalent kenge intimately verounüen wareri. After it had been washed essentially free of the soluble in salts which had arisen from the treatment processes, the slurry of coated titanium dioxide was partially dried by piltrus to form a pilter cake with a content of about 6% by weight . This iitaiiaioxyapi ^ mentbre was obtained by the method described in the Complete Specification of British Patent Application 34 "349/64 (see particularly Part 1 of Example 1). Uniform samples of this slurry of surface-coated titanium dioxide were treated as follows :

BATH ORIGINAL

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a) Mese sample was dried at 12O ⁰ G for 16 hours and then ground in a hydraulically operated]) liühle (fluid energy mill).

B) a sample of the pulp was mixed in a paste mixer with 0.3; ° pentaerythritol, based on the weight of the pigment, the pentaerythi-it was dissolved as a solution in the smallest amount of water. meanwhile the addition inne-rha3b des jireies was distributed rriichlich. The mixture was ^{dried at 12O 0} C and in a hydraulically operated trash / grinders. Samples were also in a ^-: manufactured ihnlj chen manner rei.taery uhritr.usätzen of 1.0) j 'π.α 3.0 -j bcr.o ^ s on aas figment.

C) Jrei I'roben ces Pignei.tec v.-urce · ,, vie in work · .. eifce: :) with the addition of ve; -: C, j> ev. .- ·; .-, 1, -J- Gev; .-> j and 3.0 Gev /.-^ ö before. ■ produced letriar.eth.v.olcyclohexanol, welcheb in the smallest IIen,; e water before Addition ^ u dor. is free in the niche direction had been.

L) Three more samples were made, ie in procedure B) with the addition of 0.3% by weight, 1.0% by weight and 3.0% by weight

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of technical tetramethylolmethy. ! cyclohexanol (a Liquid), based on the pigment, is produced directly in the mixing device.

¹ dried milled samples were then incorporated into polystyrene, in which a mixture of granulated polystyrene and Titandioxydpigment with a content of 1.0 ° / i> pigment, based on the weight of the polystyrene were mixed for 10 minutes by mixing in a tumbler, whereupon the register was ^{injection molded at 150 0} under a pressure of about 351.5 at (2.5 tons per suuare inch). The resulting molded disks were hot-pressed at a pressure of about 2109.2 at (15 tons per square inch) for 20 seconds between machined plates at a surface temperature of 225 ° C., thin films of uniform thickness being obtained. The pigmented films were compared visually for opacity and were assigned a rating for opacity as shown in Table 1 below, with the value 5 being assigned to the lowest opacity and the value 1 being assigned to the greatest opacity, and interpolation interpolated sina. For out of the same

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Sample of pulp made from coated titanium dioxide samples This rating also applies to the rating for the Pail one Dispersion (so "1" indicates greater dispersibility and opacity than "2", etc.)

Table 1

Additional opacity

-io ) rating

no 5

0.3 '■'' pentaerythritol 5

1.0> a "3

3, ü ₇ o »4

0.3 / o TI-IC 3

1.0 i "2

3.0, .ο "2

0.3> TMMC 2

1.0 # »1

3.0 io » 4

BATH
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-H-

Example 2
t ■

A titanium dioxide pigment was provided in a known manner with a surface coating with 1.5> hydrated titanium dioxide, 1.0 ^l / a hydrated silicon dioxide and 1.5> hydrated aluminum oxide (calculated as oxides, based on the weight of the pigment). After washing substantially free of soluble salts, the coated TiOp slurry was dehydrated to form a pilter cake of about 60 % pesticide content. This pigment slurry was obtained by the same procedure as described in Example 1. Uniform samples of this pigment slurry were treated with tetramethylolcyclohexanol and tetramethylolmethylcyclohexanol at 0.25% by weight and 1.0% by weight concentration as described in Example 1, and an untreated sample was also dried and in a hydraulically operated mill ground.

The one made by grinding in a ball mill Dispersion of these pigments was tested in the following way.

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90 g of TiOp were mixed with 22.5 [ζ linseed oil with a viscosity of 4 poise at 2O ⁰ C and .22.5 g of a mixture of white spirit (white spirit) dna'Xylene in a weight ratio of 3 ι 1 in a glass flask with a Absorbing capacities of about 236.8 cm (ole fluid ounces) and 150 grams of about 0.95 cm (3/8 inch) branded "Steatite" balls were added. The flask was on rollers at a speed of -10u rev / niiüi. rotated during 1 \ / 1 hours and the dispersion of the "" i ^ iuentes vmrde to waste a Hegman hate it v.io below ir.it in connection the "Kady" -Misch test ^{(r |} Kacy "! -mill- The fourth of the film thickness in microns, at which agglomerates begin to protrude through every paint film surface, are given in the following label II.

¹¹ ^ o-gloss "value and the hiding power of air-drying ae'i) acrylic resin drives with a content of 37 wt .- ^ of the figments are also given in Table II

I: -: α reader table was the blind or * control sample of the _i:; compensate Nischbelianälun .-- ,. how to incorporate de .. · - or. --Uilsch treated by means of the pigment carried out v / u.rde, subjected.

BATH

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Treatment agents

Table II

Ball mill opacity dispersion test sq.ft./imp. (1 1/2 hours) gallon

Control 0.25 ⁰ A I ¹ MC 1.0 Jb TKC 0.25 5 & TMIiC 1.0 <jo Ί'ΜΚΟ 0.25 # Pentaerythritol 1.0 £ "

Glan:

19 ν-
10 ** ■ 378
407 54
64 24 </ -
ί 436 63 8 / A 436 63 11 μ 407 66 27 y * 385 50 13 A * 378 52

Example 3

A liutil-Titanaioxyd pigment produced by vapor phase oxidation of titanium tetrachloride was treated with a surface coating with 1.0, Ό hydrated alumina and 1.0 fö hydrated titaniums'; ioxyd, calculated in each case as ΑΙ, λ), UIID TiO ^ "based on the Due to the pigment) mistake. After the egg washing stage, the pigment paste was treated with 0.5 wt.? * Or 1.0 wt.

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BAD GRiGlNAL

hexanol, as described in Example 1, treated, the dried samples, including one dried sample of an untreated free in a hydraulically operated mill. The resulting pigments were rated in terms of dispersibility in a. Surface coating medium tested as follows:

225 parts by weight of the pigment were mixed with 215 parts by weight of an oil paint from a linseed oil / '- pentaerythritol moctified Alkyd resin, soya lecithin oil and white spirit in weight ratios of 100: 20: 570 each mixed, mixing in a high speed dispersion paint mixer, known as the "Kady" mixer. After a mixing time of 7 minutes a sample of the paint was taken and measured with a Hegmann meter for fineness checked. The values in Table III give the depth (thickness) of the paint film in microns at which agglomerates begin by the

"Ad on""* ¹ · 009887/161 1

Ai stick film to step through :. The smaller aie The thickness, the better the dispersion of the

Pigment in the medium.

The results are compared in Table III below.

^iU , i gloss "value and the hiding power of air-drying acrylic resin paints with a content of 37 G-ew.-yo of pigments are also given in Table III.

dragonfly III

commercial dispersion mixer hiding power medium high speed

ability (7 min.)

control

0.5 # TMC

1.0 i> TMO

0.5 Io TMO

1.0 Io TMIiO

$ 1.0> Pentaerythritol 25 μ

31 μ.
I. 19th 23 μ 25th r 15th μ

Hiding power
sq.ft./lrap.
Gallon shine
5 * 436 60 450 76 472 76 443 68 450 . 73 458 74

BAD OfHGiNAL

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Claims (1)

Pat ei: tan sayings 1. Method of treating a pigment, thereby characterized in that the particles of the pigment with a compound of the cycloalkane series has a content of a hydroxyl group bonded directly to a ring carbon atom and at least 2 hydroxyalkyl groups in brings touch. 2. The method according to claim 1, characterized in that? is t-ie treatment with a compound executes "the ten-substituer by a ode :: ¹ more additional hydroxyl groups at iting, halogen atom, alkyl groups, amino groups or two or more solder substituted. 3. The method according to any one of claims 1 or 2, characterized characterized in that the treatment is carried out with a compound which has one or two hydroxyalky groups BORING COLUMN: Contains substance atom in the King. 4. The method according to any one of claims 1 to 3, characterized / eivennzeiür?; et that one can treat with a compound with at least one at eir. _: ii:; -; carbon fatom that one adjacent to a hydroxyl group-bearing king carbon atom is, rebundenen Ilydroxyalkylgruppe carries out. BAD CftiGINAL 009887/161 1 5. The method according to any one of claims 1 "to 4, characterized characterized in that the pigment particles with a Polyalkylolcyclohexanoft or a Polyalkylolcyclopentanol brings in touch. '6. Process according to Claim 5, characterized in that the treatment is carried out with a compound Alkylol groups contain up to 3 carbon atoms. 7. The method according to claim 5, characterized in that that the treatment is carried out near a continuation, whose Alkylene radical in the alkylol group is methylene, 8. The method according to buckets of claims 5-7, characterized in that the treatment with a Verbinuung executes, which contains two to four alkylol groups. 9. The method according to any one of claims 1 to 7, characterized characterized in that the treatment with a compound of the general formula executes, in which H represents a substituted or unsubstituted cyclopenta1 or cyclohexyl radical, η 1,2 or 3 and m 2,3 or 4 and the hydroxyl group on the left side of the formula directly to a king carbon atom is bound. BATH 009887/161 1 1Oo method according to claim 9, characterized in that that the treatment is carried out with a compound in which K is substituted by one or more alkyl groups is. 11. The method according to claim 9> characterized in that that you can treat with a compound of general Formulas Ί0 (CH ₀ ) ■ 0 ' 2'x ii II ^G \ / (CH ₂ J _x OH (CH ₂ ) _x OH ^or H. R ₂ HOI H ₂ O- 2'x CH, ^S 0H , (CH ₉ ) OH executes, in which lt., K ₂ and H. ,, which can be the same or different, each represent a hydrogen atom or an alkyl radical and χ is 1, 2 or 3. 12. The method according to claim 1, characterized in that the treatment with 2,2,6,6-tetramethylolcyclohexanol or 2,2, b, 6-tetramethylol-4-methylcyolohexanol BATH ORIGINAL 009887/161 1 executes. 13. The method according to claim 1, characterized in that that the treatment with 2,2,5,5-tetramethylolcyclopentanol, 2, 2,6,6-tetramethylol-; 5,4-dimethylcyclohexanol or others 2,2,6,6-tetra- (3-hydroxypropyl) -cyclohexanol executes " 14. The method according to any one of claims 1 to 13, characterized in that the pigment is treated..nit 0.01 to 5 ^c / o of the compound, based on the weight of the pigment. 15. The method according to claim 14, characterized in that the pigment is treated with υ, 1 to 1.0 yo of the compound, based on the weight of the pigment. 16 . Process according to one of Claims 1 to 15 », characterized in that the pigment treated is titanium dioxide or a colored pigment containing titanium dioxide. 17β Method according to claim 16, characterized in that that one ala pigment titanium dioxide with a surface coating treated from one or more hydrated metal oxides. 18. The method according to any one of claims 1 to 15, daduroh characterized in that the pigment is silicon dioxide BATH ORIGINAL 009887/1611 B'-irium sulphate, lithopon, barium carbonate, zirconium oxide, zinc oxide, aluminum oxide, chrome yellow or phthalocyanine treated. 19. Method r.ac "- one of claims 1 to 18, daduroh marked da'j the pigment particles with dealt with a solution of the connection. 20. The method according to claim 19> characterized in that that the pigment particles are treated with a solution of the compound in alcohol, acetone or water. 21. The method according to any one of claims 1 to 20, characterized in that the pigment particles before the treatment with the connection with water for education a paste, a paste or a slurry mixes. 22. The method according to any one of claims 1 to 1d, characterized characterized by making the compound a pulp made of titanium dioxide pigment provided with an outer surface coating adds, the slurry adding a solids content of 30 to 65 & ew .- ^ i). 23. The method according to claim 22, characterized in that one area of the pigment with the compound a pesticide content of 60 G-Ew .- # adds. BATH ORIGINAL 009887/1611 24 · The method according to any one of claims 21 to 23, characterized in that the paste, the pulp or forms the slurry in a paste mixer. Process according to one of Claims 1 to 24, characterized in that the treated pigment particles are dried ^{by heating to a temperature within a range from 100 to 180 ° C.} ■ 26. A process according to any one of claims 1 to 24, characterized in that the treated pigment is dried by heating at a temperature within the range of from 1O5 ° C to 13O ⁰ C. 009887/1611